Composition and treatment agent

ABSTRACT

A composition comprising (A) a copolymer which comprises (I) repeating units which are derived from a monomer having a fluoroalkyl group, a carbon-carbon double bond, (II) optional repeating units which are derived from a monomer having at least two urethane or urea bonds and a carbon-carbon double bond, but no fluorine atom, (III) optional repeating units which are derived from a monomer, the homopolymer of which having a glass transition temperature (Tg) of 50° C. or less, (IV) optional repeating units which are derived from a monomer having a hydrophilic group and a carbon-carbon double bond, and (V) optional repeating units which are derived from a monomer having a chlorine atom and a carbon-carbon double bond; and (B) a film-forming auxiliary can impart high water and oil repellency by drying at room temperature (0 to 30° C.) without requiring a heat treatment step.

This application is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/JP98/00334 which has an Internationalfiling date of Jan. 28, 1998 which designated the United States ofAmerica.

FIELD OF THE INVENTION

The present invention relates to a novel composition, a water and oilrepellent and a water and oil repellent product.

RELATED ART

A conventional water and oil repellent required a heat treatment at 100°C. or more as an essential step to impart high water and oil repellency,but various water and oil repellents have been proposed to improveprocessability of the water and oil repellents.

Japanese Patent Kokoku Publication No. 67511/1988 discloses a polymerobtained by binding a branch segment having a blocked fluoroalkyl groupto a trunk segment of a diene copolymer, and Japanese Patent KokaiPublication No.71977/1983 discloses that a copolymer comprising amonomer having a fluoroalkyl group and a cross-linking monomer as anessential component is a water and oil repellent which imparts highwater and oil repellency in a heat treatment step at low temperature.However, when both of them are dried at room temperature, the water andoil repellency is insufficient.

Furthermore, U.S. Pat. No. 5,350,795 discloses that a compositioncomprising fluoroacrylate/polyalkyleneglycol(meth)acrylate/polyalkyleneglycol di(meth)acrylate copolymer andRf-containing polyalkoxypolyurethane is a water and oil repellent whichimparts high water and oil repellency when it is dried at roomtemperature. However the water repellency is insufficient.

A conventional water and oil repellent requires a heat treatment as anessential step to impart high water and oil repellency, and sufficientwater and oil repellency could not be imparted without a heat treatment.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a composition whichimparts high water and oil repellency only by drying at room temperature(0 to 30° C.) without requiring a heat treatment step.

Another object of the present invention is to provide a water and oilrepellent product or article comprising said composition.

The present invention provides a composition comprising

(A) a binary or more copolymer which comprises

(1) repeating units which impart water and oil repellency,

(2) repeating units which impart a solubility in a firm-formingauxiliary,

(3) optional repeating units which lower the glass transitiontemperature of the polymer, and

(4) optional repeating units which impart an affinity with a substrate,and

(B) a film-forming auxiliary consisting of an organic solvent whichdissolves or swells the copolymer.

DETAILED DESCRIPTION OF THE INVENTION

Repeating units (1) which impart water and oil repellency may be (I)repeating units which are derived from a monomer having a fluoroalkylgroup, a carbon-carbon double bond, and optionally a urethane or ureabond.

Repeating units (2) which impart solubility in (or compatibility with) afilm-forming auxiliary may be (II) repeating units which are derivedfrom a monomer having a urethane or urea bond and a carbon-carbon doublebond, but no fluorine atom; or (III) repeating units which are derivedfrom a monomer having a carbon-carbon double bond, the homopolymer ofsaid monomer having a glass transition temperature (Tg) of at most 50°C.

Repeating units (3) which lower the glass transition temperature of thepolymer may be (III) repeating units which are derived from a monomerhaving a carbon-carbon double bond, the homopolymer of said monomerhaving a glass transition temperature (Tg) of at most 50° C.

Repeating units (4) which impart an affinity with a substrate may be(IV) repeating units which are derived from a monomer having ahydrophilic group and a carbon-carbon double bond, or (V) repeatingunits which are derived from a monomer having a chlorine atom and acarbon-carbon double bond.

The present invention provides a composition comprising

(A) a copolymer which comprises

(I) repeating units which are derived from a monomer having afluoroalkyl group, a carbon-carbon double bond, and optionally aurethane or urea bond,

(II) optional repeating units which are derived from a monomer having aurethane or urea bond and a carbon-carbon double bond, but no fluorineatom,

(III) optional repeating units which are derived from a monomer having acarbon-carbon double bond, the homopolymer of said monomer having aglass transition temperature (Tg) of 50° C. or less,

(IV) optional repeating units which are derived from a monomer having ahydrophilic group and a carbon-carbon double bond, and

(V) optional repeating units which are derived from a monomer having achlorine atom and a carbon-carbon double bond and

(B) a film-forming auxiliary consisting of an organic solvent whichdissolves or swells the copolymer,

wherein at least one of the repeating units (II) and the repeating units(III) is essential in the copolymer (A).

The composition of the present invention is suitable for a treatmentagent, in particular a water and oil repellent.

The repeating units (I) are essential in the copolymer (A). Therepeating units (II), the repeating units (III), the repeating units(IV) and the repeating units (V) are optional repeating units which haveno need to be present. But at least one of the repeating units (II) andthe repeating units (III) is essential.

The copolymer (A) in the composition of the present invention may be,for example:

(a) a copolymer having the repeating units (I) and (II),

(b) a copolymer having the repeating units (I) and (III),

(c) a copolymer having the repeating units (I), (II) and (III),

(d) a copolymer having the repeating units (I), (II) and (IV) and/or(V),

(e) a copolymer having the repeating units (I), (III) and (IV) and/or(V), or

(f) a copolymer having the repeating units (I), (II), (III) and (IV)and/or (V).

The present invention provides a copolymer wherein the repeating units(I), the repeating units (II) and the repeating units (III) areessential, and the repeating units (IV) and the repeating units (V) areoptional.

In the repeating units (I) a fluoroalkyl group is preferably aperfluoroalkyl group.

The repeating units (I) are preferably repeating units which are derivedfrom (meth)acrylic ester containing a fluoroalkyl group. A monomer whichconstitutes the repeating units (I) is preferably a compound of theformula:

Rf—R¹—OCOC(R²)═CH₂

wherein Rf is a linear or branched fluoroalkyl group having 3 to 20carbon atoms;

R¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, agroup of the formula: —SO₂N(R³)R⁴— or a group of the formula:—CH₂CH(OR⁵)CH₂— in which R³ is an alkyl group having 1 to 10 carbonatoms, R⁴ is a linear or branched alkylene group having 1 to 10 carbonatoms, and R⁵ is a hydrogen atom or an acyl group having 1 to 10 carbonatoms; and

R² is a hydrogen atom or a methyl group.

Examples of the monomer (I) having a fluoroalkyl group are not limitedto, but include the followings:

CF₃(CF₂)₇(CH₂)₁₀OCOCCH═CH₂

CF₃(CF₂)₇(CH₂)₁₀OCOC(CH₃)═CH₂

CF₃(CF₂)₆CH₂OCOCH═CH₂

CF₃(CF₂)₈CH₂OCOC(CH₃)═CH₂

(CF₃)₂CF(CF₂)₆(CH₂)₂OCOCH═CH₂

(CF₃)₂CF(CF₂)₈(CH₂)₂OCOCH═CH₂

(CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOCH═CH₂

(CF₃)₂CF(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂

(CF₃)₂CF(CF₂)₈(CH₂)₂OCOC(CH₃)═CH₂

(CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOC(CH₃)═CH₂

CF₃CF₂(CF₂)₆(CH₂)₂OCOCH═CH₂

CF₃CF₂(CF₂)₈(CH₂)₂OCOCH═CH₂

CF₃CF₂(CF₂)₁₀(CH₂)₂OCOCH═CH₂

CF₃CF₂(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂

CF₃CF₂(CF₂)₈(CH₂)2OCOC(CH₃)═CH₂

CF₃CF₂(CF₂)₁₀(CH₂)₂OCOC(CH₃)═CH₂

CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOCH═CH₂

CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₂OCOCH═CH₂

(CF₃)₂CF(CF₂)₈CH₂CH(OCOCH₃)CH₂OCOC(CH₃)═CH₂

(CF₃)₂CF(CF₂)₆CH₂CH(OH)CH₂OCOCH═CH₂

The monomer (I) having a urethane or urea bond and a fluoroalkyl groupmay be a compound of the general formula:

Rf¹—X¹—A¹—CONH—Y¹—NHCO—A²—O—C(═O)—CR³═CH₂

wherein Rf¹ is a fluoroalkyl group having 4 to 16 carbon atoms;

X¹ is —R¹—, —CON(R²)—Q¹— or —SO₂N(R²)—Q¹—, in which R¹ is an alkylenegroup, R² is a hydrogen atom or a lower alkyl group and Q¹ is analkylene group;

A¹ is —O—, —S— or —N(R²)—, in which R² is a hydrogen atom or a loweralkyl group;

Y¹ is a residue remaining by removing an isocyanate from an aromatic oralicyclic diisocyanate;

A² is a bivalent organic group having 2 to 9 carbon atoms and capable ofcontaining at least one oxygen atom; and

R³ is a hydrogen atom or a methyl group.

Specific examples of the monomer (I) having a urethane or urea bond anda fluoroalkyl group are as follows:

A monomer having a urethane or urea bond and a fluoroalkyl group, whichconstitutes the repeating units (I), may be a monomer obtained byreacting

(I-a) a compound having at least two isocyanate groups,

(I-b) a compound having one carbon-carbon double bond and at least onehydroxyl or amino group, and

(I-c) a compound having a fluoroalkyl group and one hydroxyl or aminogroup; or

a monomer obtained by reacting a compound having one isocyanate groupand at least one carbon-carbon double bond with the compound (I-c).

The monomer (II) having a urethane or urea bond and a carbon-carbondouble bond, but no fluorine atom may be a monomer obtained by reacting

(II-a) a compound having at least two isocyanate groups, and

(II-b) a compound having one carbon-carbon double bond and at least onehydroxyl or amino group with (II-c-1) a compound having at least onehydroxyl or amino group, and a polyoxyalkylene chain or a polysiloxanechain, or

(II-c-2) a compound having at least one hydroxyl or amino group; or

a monomer obtained by reacting a compound having one isocyanate groupand at least one carbon-carbon double bond with the compound (II-c-1) or(II-c-2).

Examples of the compound (II-a) are as follows:

The compound (II-a) is preferably diisocyanate. But triisocyanate andpolyisocyanate can be also used for the reaction.

For example, a trimer of diisocyanate, polymeric MDI(diphenylmethanediisocyanate) as well as an adduct of polyhydricalcohols such as trimethylol propane, trimethylol ethane and glycerin toa diisocyanate can be also used in the reaction.

Examples of triisocyanate and polyisocyanate are as follows:

The compound (II-b) may be, for example, a compound of the formula:

wherein R¹ is a hydrogen atom or a methyl group, p is a number of 1 to300 (e.g. 1 to 20) and X is as follows:

wherein p, m and n are a number of 1 to 300, respectively.

The compound (II-c-1) may be a compound of the formula:

R¹—(O—R²)_(n)—OH

R¹—(O—R²)_(n)—NH₂

wherein R¹ represents a hydrogen atom or a C₁ to C₂₂ alkyl group, in thelatter case a hetero atom, or an aromatic or an alicyclic compound maybe contained; R² represents a linear or branched C₁ to C₆ alkylenegroup; R³ and R⁴ represents a hydrogen atom or a C₁ to C₆ alkyl groupwhich optionally contains a hetero atom, or an aromatic or an alicycliccompound, or optionally contains a modification such as fluorinemodification, polyether modification, alcohol modification, aminomodification, epoxy modification, epoxy ether modification, phenolmodification, carboxyl modification, and mercapto modification; and nrepresents an integer of 1 to 50. Preferred R¹, R³ and R⁴ groups are CH₃and preferred R² group is C₂H₄ and C₃H₆.

Examples of the compound (II-c-1) are polyethylene glycol monomethylether, polypropylene glycol monomethyl ether, end silanol group dimethylsilicone and end amino-modified dimethyl silicone.

The compound (II-c-2) has neither of a polyoxyalkylene chain nor apolysiloxane chain. The compound (II-c-2) may be a compound of theformula:

R²—OH

R²—NH₂ or

R²—NH—R³

wherein R² and R³, the same or different, represent a C₁ to C₂₂ alkylgroup and optionally contain a hetero atom, or an aromatic or analicyclic compound. Preferred R² and R³ groups are C₈H₁₇, C₁₈H₃₇, C₄H₉and cyclohexyl.

Examples of the compound (II-c-2) include butyl alcohol, 2-ethylhexylalcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol,cyclohexyl alcohol, 2-ethylhexylamine and stearylamine.

The compound (II-a), (II-b) and (II-c-1) or (II-c-2) are reacted inamounts of, when (II-a) is diisocyanate, one mol of (II-b) and (II-c-1)or (II-c-2) per one mol of (II-a), and when (II-a) is triisocyanate, onemol of (II-b) and two mols of (II-c-1) or (II-c-2) per one mol of(II-a).

A monomer which constitutes the repeating units (III) may be a monomerhaving conjugated double bonds or one or two carbon-carbon double bonds,and a glass transition temperature (Tg) of 50° C. or less, for example30° C. or less, particularly 0° C. or less.

The term “a monomer having a glass transition temperature (Tg) of 50° C.or less” means that the homopolymer consisting of said monomer has aglass transition temperature (Tg) of 50° C. or less. Tg was measured byusing DSC, Model 7 manufactured by Perkin Elmer Co.

A monomer which constitutes the repeating units (III) is preferably adiene monomer, a (meth)acrylic ester monomer or a di(meth)acrylic estermonomer.

The (meth)acrylic ester monomer may be a compound of the generalformula:

CH₂═CA¹COOA²

or

CH₂═CA¹COO(R¹—O)_(n)—A²

wherein A¹ is a hydrogen atom or a methyl group,

A² is a linear or branched C₁ to C₃₀ alkyl group,

R¹ is a linear or branched C₁ to C₆ alkylene group and

n is an integer of 1 to 30.

The di(meth)acrylic ester monomer may be a compound of the generalformula:

CH₂═CA¹COO(R¹)_(n)OOCA¹C═CH₂

or

 CH₂═CA¹COO(R¹—O)_(n)—OCA¹C═CH₂

wherein A¹ is a hydrogen atom or a methyl group,

R¹ is a linear or branched C₁ to C₆ alkylene group, and

n is an integer of 1 to 30.

Examples of the monomer having a glass transition temperature of 30 to50° C. include cetyl acrylate and isobutyl methacrylate for examples ofthe (meth)acrylic ester monomer; and polyethylene glycol(4)diacrylatefor examples of the di(meth)acrylic ester monomer.

Examples of the monomer having a glass transition temperature of 0 to30° C. include methyl acrylate, n-butyl methacrylate, and cetylmethacrylate for examples of the (meth)acrylic ester monomer.

Examples of the monomer having a glass transition temperature of 0° C.or less include isoprene and 1,3-butadiene for examples of the dienemonomer; and ethyl acrylate, n-butyl acrylate, n-octyl acrylate,2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate for examples of the(meth)acrylic ester monomer.

A monomer which constitutes the repeating units (IV) and has ahydrophilic group and a carbon-carbon double bond may be, for example acompound of the formula:

CH₂═CA¹—C(═O)—X¹—A²

wherein A¹ is a hydrogen atom or a methyl group,

X¹ is —O—, —CH₂— or —NH—,

A² is a hydrogen atom, a hydrophilic group or a group containing ahydrophilic group.

Examples of the hydrophilic group include a hydroxyl group, a glycidylgroup, an ester group, an amine group, a urethane group, a phosphategroup, a sulfate group and the like.

Examples of the monomer which constitutes the repeating units (IV)include glycidyl methacrylate, hydroxypropyl methacrylate,2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl acrylate, glycerolmonomethacrylate, β-acryloyloxyethyl hydrogen succinate,β-methacryloyloxyethyl hydrogen phthalate,2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethylphthalicacid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, hydroxypropylmethacrylate trimethylammonium chloride, dimethylaminoethylmethacrylate, diethylaminoethyl methacrylate, 2-acryloyloxyethyl acidphosphate, glucosylethyl methacrylate, methacrylamide,2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxy-3-acryloyloxypropylmethacrylate, 2-methacryloyloxyethyl acid phosphate and neopentyl glycolhydroxypivalate diacrylate.

A monomer which constitutes the repeating units (V) and has a chlorineatom and a carbon-carbon double bond may be, for example, a compound ofthe formula:

CY¹Y²═CY³—Z

wherein Y¹ and Y² is respectively a hydrogen atom or a fluorine atom,

Y³ is a hydrogen atom, a fluorine atom, a chlorine atom or a methylgroup,

Z is a chlorine atom or a chlorine atom-containing group.

Examples of the chlorine-containing monomer which constitutes therepeating units (V) include vinyl chloride, vinylidene chloride,3-chloro-2-hydroxypropyl methacrylate and monochlorotrifluoroethylene.

A weight average molecular weight of the copolymer (A) is preferablyfrom 2,000 to 1,000,000.

The amount of the repeating units (I) is preferably from 40 to 90% byweight,

and more preferably from 50 to 80% by weight,

the amount of the repeating units (II) is 60% by weight or less, e.g.from 5 to 60% by weight, and more preferably from 10 to 50% by weight,

the amount of the repeating units (III) is 60% by weight or less, e.g.from 1 to 60% by weight, and more preferably from 1 to 50% by weight,

the amount of the repeating units (IV) is 30% by weight or less, andmore preferably from 0.1 to 20% by weight, and

the amount of the repeating units (V) is 30% by weight or less, and morepreferably from 0.1 to 20% by weight,

based on the amount of the copolymer (A).

The film-forming auxiliary (B) which facilitates the film-forming of thecopolymer (A) by existing together with the copolymer (A) is preferablythose which dissolves, swells or softens the copolymer (A).

The film-forming auxiliary (B) may be (i) an alcohol, glycol ether,ketone, ether and ester having a C₁ to C₂₂ alkyl chain, or (ii) a linearor cyclic silicone.

The film-forming auxiliary (B) (i) may be a compound containing afluorine atom, a hetero atom, an aromatic ring or an aliphatic ring.

The film-forming auxiliary (B) (ii) may be a compound of the formula:

wherein R⁹ and R¹⁰ each represents a hydrogen atom or a C₁ to C₆ alkylgroup, which optionally contains a hetero atom, an aromatic or analicyclic compound, or optionally contains a modification such asfluorine modification, polyether modification, alcohol modification,amino modification, epoxy modification, epoxy ether modification, phenolmodification, carboxyl modification and mercapto modification; and nrepresents a number of 1 to 50.

As the film-forming auxiliary (B), a compound having the value of thesolubility parameter (sp) at 25° C. of 5 to 15, e.g. 8 to 11 issuitable. The solubility parameter is calculated according to Fedors'method (R. F. Fedors, Polym. Eng. Sci., 14(2), 147(1974)).

The role of the film-forming auxiliary is to dissolve, swell or softenthe copolymer (A) and induce film-formation of the copolymer (A) with alow calorie. This makes it possible to impart high water and oilrepellency without requiring any heat treatment step. The film-formingauxiliary may be single compound or two or more of them may be used incombination. The film-forming auxiliary may be the same as or differentfrom the polymerization solvent.

Examples of the film-forming auxiliary (B) include, for example,ethanol, dipropylene glycol monomethyl ether, 1-methoxy-2-propanol,diethylene glycol acetate monoethyl ether, di-n-butyl adipate, butylcarbitol acetate, octamethyltrisiloxane anddecamethylcyclopentasiloxane.

The composition of the present invention may comprise 30 to 99.9 partsby weight, particularly 40 to 95 parts by weight, e.g. 50 to 80 parts byweight of the copolymer (A) and 0.1 to 70 parts by weight, particularly5 to 60 parts by weight, e.g. 20 to 50 parts by weight of thefilm-forming auxiliary (B).

The copolymer can be prepared by emulsion polymerization, solutionpolymerization or suspension polymerization. In particular, the emulsionpolymerization is preferred.

The copolymer of the present invention can also be produced in anaqueous emulsion. Monomers are emulsion-polymerized by use of water, anemulsifying agent and optionally an organic solvent. The film-formingauxiliary (B) may be added before or after the emulsion polymerization.The mixture may previously be emulsified by a high-pressure emulsifyingmachine or the like before polymerization.

The emulsifying agent used may be any type of a surface active agent,such as an anionic, cationic or nonionic surface active agent.

Examples of the anionic surface active agent include sodium laurylsulfate, lauryl sulfate triethanolamine, sodium polyoxyethylene laurylether sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate,polyoxyethylene lauryl ether sulfate triethanolamine, sodium cocoylsarcosine, sodium N-cocoyl methyl taurine, sodium polyoxyethylenecoconut alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodiumα-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylenelauryl ether phosphate, and perfluoroalkyl carboxylate salt (UnidineDS-101 and 102 manufactured by Daikin Industries Ltd.).

Examples of the cationic surface active agent include dialkyl (C₁₂-C₂₂)dimethyl ammonium chloride, alkyl (coconut) dimethyl benzyl ammoniumchloride, octadecyl amine acetate salt, tetradecyl amine acetate salt,tallow alkyl propylene diamine acetate salt, octadecyl trimethylammonium chloride, alkyl (tallow) trimethyl ammonium chloride, dodecyltrimethyl ammonium chloride, alkyl (coconut) trimethyl ammoniumchloride, hexadecyl trimethyl ammonium chloride, behenyl trimethylammonium chloride, alkyl (tallow) imidazoline quaternary salt,tetradecyl methyl benzyl ammonium chloride, octadecyl dimethyl benzylammonium chloride, dioleyl dimethyl ammonium chloride, polyoxyethylenedodecyl monomethyl ammonium chloride, polyoxyethylene alkyl (C₁₂-C₂₂)benzyl ammonium chloride, polyoxyethylene lauryl monomethyl ammoniumchloride, 1-hydroxyethyl-2-alkyl (tallow) imidazoline quaternary salt, asilicone-based cationic surface active agent having a siloxane group asa hydrophobic group, and a fluorine-based cationic surface active agenthaving a fluoroalkyl group as a hydrophobic group (Unidine DS-202manufactured by Daikin Industries Ltd.).

Examples of the nonionic surface active agent include polyoxyethylenelauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetylether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylenestearyl ether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenylether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate,polyoxyethylene monostearate, polyoxyethylene mono-oleate, sorbitanmonolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitanmonostearate, sorbitan mono-oleate, sorbitan sesqui-oleate, sorbitantrioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylenesorbitan monopalmitate, polyoxyethylene sorbitan monostearate,polyoxyethylene sorbitan mono-oleate, polyoxyethylene polyoxypropyleneblock polymer, polyglycerin fatty acid ester, polyether-modifiedsilicone oil (SH3746, SH3748, SH3749 and SH3771 manufactured by TorayDow Corning Silicone Co., Ltd.), perfluoroalkyl ethylene oxide adduct(Unidine DS-401 and DS-403 manufactured by Daikin Industries Ltd.),fluoroalkyl ethylene oxide adduct (Unidine DS-406 manufactured by DaikinIndustries Ltd.), and perfluoroalkyl oligomer (Unidine DS-451manufactured by Daikin Industries Ltd.).

Examples of the organic solvent used in the emulsion polymerization arethe same as the organic solvent used in the solution polymerizationdescribed hereinafter.

The copolymer of present invention can be produced by the solutionpolymerization in an organic solvent. Examples of the organic solventinclude ketones such as acetone, methyl ethyl ketone and methyl isobutylketone; esters such as ethyl acetate, propyl acetate, butyl acetate,dibutyl adipate and dibutyl succinate; alcohols such as ethanol,isopropanol, butanol, 1,3-butanediol and 1,5-pentanediol; halogenatedhydrocarbon such as perchlorethylene, trichlene,1,1-dichloro-2,2,3,3,3-pentafluoropropane,1,3-dichloro-1,2,2,3,3,3-pentafluoropropane and1,1-dichloro-1-fluoroethane (HCFC-141b); hydrocarbons such as octane,petroleum, toluene and xylene; dipropylene glycol, dipropylene glycolmonomethyl ether, tripropylene glycol monomethyl ether, polypropyleneglycol, triethylene glycol dimethyl ether, propylene glycol and ethyleneglycol.

The preferred organic solvents are ketones such as methyl ethyl ketoneand methyl isobutyl ketone; ethyl acetate, 1,1-dichloro-1-fluoroethaneand the like.

In polymerization, a polymerization initiator, an ionizing radiationsuch as γ-ray and the like is used to initiate the polymerization.Examples of the polymerization initiator are an organic peroxide, an azocompound, a persulfate salt and the like.

Examples of the organic peroxide include t-butyl peroxy pivalate,benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide and diisopropylperoxy dicarbonate. Examples of the azo compound include2,2′-azobisisobutyronitrile,2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis(2-methylbutaneamidooxime)dihydro-chloride and2,2′-azobis(2-methylbutyronitrile).

The copolymer of the present invention can be used as a treatment agent.The treatment agent may be a water and oil repellent. The treatmentagent comprises the copolymer and the film-forming auxiliary, anoptional polymerization solvent and diluting solvent. The dilutingsolvent may be water, an alcohol (e.g. alkanol), a ketone, an ester, anether (e.g. a glycol ether) or a mixture of them. In particular, thediluting solvent is preferably water. The film-forming auxiliary, thediluting solvent and the polymerization solvent may be different oneanother. When the diluting solvent and the polymerization solvent aredifferent each other, the polymerization solvent may be removed (byevaporation, etc.) before using the treatment agent.

The alcohol used as the diluting solvent includes C₁ to C₄ loweralkanols such as methanol, ethanol, 2-propanol and n-butanol. Amongthese lower alkanols, ethanol and 2-propanol are preferable in view ofsafety. Alkanols having at least five carbon atoms are not preferablebecause of poor drying characteristics. These lower alkanols can be usedsingly or in combination thereof.

Solvents such as isoparaffin, n-heptane, n-hexane, mineral terpene,ethyl acetate, toluene, methyl ethyl ketone and methyl isobutyl ketonecan be added at a less dangerous level. An alternative fluorocarbon suchas fluorocarbon 141b can also be used as a matter of course. Further,the addition of a small amount of glycol ethers such as dipropyleneglycol monomethyl ether is also effective in preventing whitening.

A wide variety of additives can be added to the treatment agent of thepresent invention according to necessity. Among the additives, anorganopolysiloxane is important because it can improve water repellency.The organopolysiloxane used may be a silicone oil, a silicone dispersionor a mixture thereof. The silicone oil is most typically dimethylpolysiloxane having various degrees of polymerization at a viscosityranging from 0.65 to 300,000 cS at 25° C., which is represented by thefollowing formula:

Further, a main chain of some organopolysiloxanes may contain a smallamount of the following group:

Other examples include those having —(CH₃CH₂)SiO—, —CH₃)HSiO—,—(C₆H₅)₂SiO—, —(C₆H₅)(CH₃)SiO— or a mixture of these groups, in place of—(CH₃)₂SiO—. Further, some organopolysiloxanes may have the terminal ofthe main chain Si—O—Si substituted with a hydroxyl group. Further, thereare a wide variety of modified silicone oil having these side chainschlorinated or being modified by introducing an amino group, epoxygroup, polyether group, carboxyl group, hydroxyl group, trifluoroalkylgroup, alcohol ester group, alkyl group or the like. The siliconedispersion is a dispersion in which silicone resin or silicone rubber atan initial stage of polymerization has been dissolved in a solvent, andit forms a film having a three-dimensional network structure throughcondensation upon heating. In the present invention, a wide variety oforganopolysiloxanes can be used without limitation to those enumeratedabove. For these organopolysiloxanes, there are many types of commercialproducts. Examples of the commercial products include SH200, PRX413,SH8011 and SD8000 (manufacture by Toray Dow Corning Silicone Co., Ltd.),KP-801M, KPN-3504 (manufactured by Shin-Etsu Chemical Co., Ltd.). Theamount of organopolysiloxane incorporated may be from about 0.05 toabout 10% by weight, preferably from about 0.5 to 5% by weight, based onthe treatment agent of the present invention.

Stain preventing agents, UV absorbents, surface active agents,disinfectants, insecticides, antistatic agents, perfumes or the like asdescribed in Japanese Patent Kokoku Publication Nos. 6163/1987 and33797/1988 may be added to the treatment agent of the present inventionaccording to necessity. In order to soften treated fabrics, to preventcharging of treated fabrics, to improve water and oil repellency and toimprove shrink-resistance, an antistatic agent, an aminoplast resin, anacrylic polymer, a natural wax, a silicone resin or the like may furtherbe added in such amounts that the effect of the present invention is notinhibited.

The treatment agent, in particular the water and oil repellent of thepresent invention may be composed of aqueous emulsion-type compositionprepared by the emulsion polymerization method.

The water and oil repellent of the present invention can be applied to asubstrate according to a conventionally known method. A method ofdispersing said water and oil repellent into an organic solvent or waterto dilute it, attaching it on the surface of the substrate by aprocedure such as dip application, spray application, foam applicationto the substrate and the like, and drying it is usually adopted. Thedrying may be carried out by allowing to stand (solar drying or shadedrying) at room temperature (0 to 30° C.) or by heat-drying with ahousehold dryer, an iron and a drier. If necessary, the curing may bealso carried out by applying the water and oil repellent together withan appropriate closslinking agent. Furthermore, in addition to the waterand oil repellent of the present invention, mothproofing agents,softening agents, anti-microbial agents, flame-retardants, antistaticagents, paint primers and crease-retardants can also be added and usedin combination. In case of the dip application, the concentration of thecopolymer in the treatment liquid may be from 0.05 to 10% by weight. Incase of the spray application, the concentration of the copolymer in thetreatment liquid may be from 0.1 to 5% by weight.

The water and oil repellent may be in the form of emulsion, aerosol,solid or paste.

The water and oil repellent may be used in a water and oil repellentproduct or article.

The water and oil repellent product may comprise, for example (a) awater and oil repellent alone, (b) a water and oil repellent and anapplication apparatus, or (c) a water and oil repellent and a containerin which the water and oil repellent is contained.

The water and oil repellent product which comprises a water and oilrepellent emulsion may be for example (i) a water and oil repellentproduct comprising a water and oil repellent which is charged in acontainer equipped with a mechanism for spraying a liquid in saidcontainer outside (for example using a trigger type container); or (ii)a water and oil repellent product comprising a water and oil repellentwhich is charged in a container equipped with a mechanism for propellinga liquid in said container outside using a pressure (for example using amanual pump container or an aerosol type container). It may be also awater and oil repellent product in the form of foam comprising theemulsion containing additionally a foaming agent which is charged in thecontainer of (i) or (ii). When a water and oil repellent product in theform of foam is used, examples of the foaming agent which is added tothe emulsion are preferably an anionic surfactant, a cationicsurfactant, an amphoteric surfactant or a nonionic surfactant which hasthe foaming property previously known.

As the anionic surfactant, for example, sodium alkyl aryl sulfonatesalt, sodium alkyl sulfuric ester salt, sodium alkyl sulfonate, sodiumdialkyl sulfosuccinate, sodium polyoxyethylene alkyl aryl ether sulfuricester, sodium polyoxyethylene alkyl ether sulfuric ester, sodiumperfluoroalkylamido-N-propionate salt and the like are preferred.

As the cationic surfactant, alkyl aryl trimethyl ammonium chloride,alkyl trimethyl ammonium chloride and alkyl dimethyl amine acetate saltare preferred.

As the amphoteric surfactant, for example, alkylbetaine andalkylimidazoline are preferred.

As the nonionic surfactant, for example, polyoxyethylene alkyl ether,polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester,polyoxyethylene alkylamide, polyoxyethylene lanolin alcohol,polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitolfatty acid ester, dimethylalkylamine oxide, bishydroxyethyl alkylamineoxide, N-alkylmorpholine oxide, polyoxyethylene fatty acid alkylolamideand sucrose ester are preferred.

Among them, the foaming agent is preferably those which have the initialfoam height of at least 30 mm at the concentration of the foamingsurfactant of 0.1% by weight at 30° C. when measuring according to thefoaming measurement method of JIS K-3362.

The amount of the foaming surfactant is preferably from 0.007 to 2 partsby weight based on 100 parts by weight of the treatment agent of thepresent invention.

The water and oil repellent is sprayed or coated to the substrate, orthe substrate is dipped into the water and oil repellent using thesewater and oil repellent products. When it is coated, a coating apparatussuch as a sponge, a roller or a brush may be used and these coatingapparatuses may be equipped in the container.

The water and oil repellent in the form of solid or paste is applied tothe substrate. The water and oil repellent product which comprises thewater and oil repellent in the form of solid may be charged in a sticktype container such that being used for a lipstick or in a box typecontainer such that being used for car wax. The water and oil repellentproduct which comprises the water and oil repellent in the form of pastemay be charged in a tube type container such that being used for adentifrice or in a box type container such that being used for car wax.When the water and oil repellent is applied, an application apparatussuch as a sponge, a roller or a brush may be used and these applicationapparatuses may be equipped in the container.

The water and oil repellent of the present invention may be used as anaerosol. The water and oil repellent of the present invention can easilyform the aerosol by adding a propellant to the stock liquid and chargingin a container. As the propellant, liquid petroleum gas (LPG), propane,butane, dimethyl ether, carbon dioxide, nitrogen gas and the like can beused. Optionally, an alternative fluorocarbon such as HFC-134a andHCFC-141b is also used. The weight ratio of the stock liquid to thepropellant is from 99.5/0.5 to 30/70, and preferably from 99/1 to 50/50.

A substrate to be treated with the water and oil repellent of thepresent invention is preferably a textile. As the textile, variousexamples can be recited. Examples of them include an animal- andvegetative-origin natural fiber such as cotton, hemp, wool and silk; asynthetic fiber such as a polyamide, a polyester, polyvinyl alcohol,polyacrylonitrile, polyvinyl chloride and polypropylene; asemi-synthetic fiber such as rayon and acetate; an inorganic fiber suchas glass fiber, carbon fiber and asbestos fiber; or a mixture of thesefibers.

The textile may be any of in the form of yarn, fabric and the like.Examples of the substrate which can be treated with the water and oilrepellent of the present invention include glass, paper, wood, leather,fur, asbestos, brick, cement, metal and metal oxide, ceramics (e.g.tile), plastic, coating surface and plaster, rubber, cork and the like,in addition to a textile.

Examples of the substrate to be treated include:

garments, for example, undergarment, hosiery, overgarment, trousers,coat, raincoat, hat, gloves, shoes, boots, kimono, formalwear, fulldress, accessory, dress shirt, necktie, belt, slippers, fastener andclothing for pet;

interiors, for example, outer packaging of light fitment, chair, sofa,table, drawer, sideboard, wall paper, wall material, tatami (Japanesemat), floor material, screen, paper screen, window screen, glass,curtain, carpet, mat and dust-bin:

kitchen apparatus, for example, range hood, sink, counter top, exhaustfan, tablecloth, dust receiver of sink, coaster and apron;

bath and toilet article, for example, bathtub, tile, basin, bath pail,toilet bowl, paper holder and bedpan;

bedclothings, for example, bed, bed pad and futon (Japanese bedding);

domestic appliances, for example, inner and outer packaging ofrefrigerator, inner and outer packaging of washing machine, outerpackaging of AV apparatus, outer packaging of telephone, outer packagingof air conditioner and outer packaging of cleaner;

travel and leisure goods, for example, suitcase, lingerie case, toiletgoods porch and cosmetic porch;

car and bike goods, for example, glass, mirror, lamp, seat, innerlining, mat, wheel, outer packaging, inner lining of trunk and wiper;

sports and outdoor goods, for example, gloves, baseball gloves, shoes,cap, wear, helmet, racket, golf club, bat, ski boards, snow board,skating board, beach goods, goggle, tent, sleeping bag, sheet, swimsuit,wetsuit, ball, bag, rucksack and fishing tackle;

other daily use sundries, for example, umbrella, bag, purse, key, outerpackaging of mobile phone, watch, eyeglasses, sunglasses, pocket datebook, buisiness card, toy, book, outer packaging of game machine, petgoods, instrument, baby bogie, tricycle and bicycle; and

facility, for example, outer packaging of post and telephone box.

PREFERRED EMBODIMENTS OF THE INVENTION

The following Examples and Comparative Examples further illustrate thepresent invention in detail. In the Examples and Comparative Examples,parts and percentage are by weight unless otherwise stated.

Water repellency and oil repellency shown in the Examples andComparative Examples are expressed by the following evaluations. Waterrepellency is expressed in terms of water repellency No. (see Table 1below) by a spray method in accordance with JIS (Japenese IndustrialStandard) L-1092. Oil repellency is expressed in terms of oil repellencyNo. by observing the state whether the drop can be maintained on thecloth for 30 seconds after one drop (about 5 mm in diameter) of a testsolution shown in Table 2 below is placed on a sample cloth (AATCCTM118-1992). The symbol “+” assigned to water repellency No. indicatesslightly good performance and the symbol “−” indicates slightly poorperformance.

TABLE 1 Water repellency No. State 100  No wet on the surface 90 Slightwet on the surface 80 Partial wet on the surface 70 Wet on the surface50 Wet on the whole surface  0 Complete wet on the front and backsurfaces

TABLE 2 Oil repellency Surface tension No. Test solution (dyne/cm, 25°C.) 8 n-Heptane 20.0 7 n-Octane 21.3 6 n-Decane 23.5 5 n-Dodecane 25.0 4n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 Mixture of n-hexadecane/nujol(35/65) 29.6 1 Nujol 31.2 0 inferior to 1 —

The preparation of the monomer (I) or (II) having a urethane bond isshown in Preparative Examples 1 to 3.

PREPARATIVE EXAMPLE 1 (PREPARATION OF THE PRODUCT U1)

In a flask equipped with a stirrer, a thermometer, a reflux condenserand a dropping funnel, 348 g of 2,4-tolylene diisocyanate was dissolvedin 348 g of methyl isobutyl ketone (MIBK) and heated to 80° C. withpurging with nitrogen and stirring. When the temperature of the mixturereached 80° C., two drops of dibutyltin laurate was added and, at thesame time, dropwise addition of 260 g of perfluoroalkylethyl alcohol (aperfluoroalkyl group is CF₃(CF₂)_(n) (the average of n is 3.5)) wasstarted and it was gently added dropwise over two hours. After thecompletion of the dropwise addition, 260 g of 2-hydroxyethylmethacrylate was gently dropped over two hours. After the completion ofthe dropwise addition, the stirring was continued for additional twohours with maintaining at 80° C. Then, MIBK was distilled off underreduced pressure to give 868 g of pale yellow and transparent viscousliquid. Complete disappearance of a —NCO group was confirmed by IR anddisappearance of a —OH group, formation of a urethane bond and presenceof a double bond were confirmed by ¹H-NMR and ¹³C-NMR. This product wasnamed as U1.

The chemical formula of the product U1 was considered as follows:

wherein Rf is a perfluoroalkyl group.

PREPARATIVE EXAMPLE 2 (PREPARATION OF THE PRODUCT U2)

The reaction was conducted in the same manner as Preparative Example 1except that dipropylene glycol monomethyl ether was added dropwiseinstead of perfluoroalkylethyl alcohol. This product was named as U2.

The chemical formula of the product U2 was considered as the following:

wherein n is 2.

PREPARATIVE EXAMPLE 3 (PREPARATION OF THE PRODUCT U3)

The reaction was conducted in the same manner as Preparative Example 1except that end silanol group-containing polydimethyl siloxane was addeddropwise instead of perfluoroalkylethyl alcohol. This product was namedas U3.

The chemical formula of the product U3 was considered as follows:

wherein the average of n is 10.

The monomers shown in Table 3 were used in the following PreparativeExamples.

TABLE 3 Monomer a

Monomer b

PREPARATIVE EXAMPLE 4

35 g of U1 (a fluorine- and urethane bond-containing monomer)synthesized in Preparative Example 1, 10 g of the monomer a (a urethanebond-containing monomer) shown in Table 3, 5 g of isoprene, 1 g oflauryl mercaptan, 1.5 g of sodium α-olefin sulfonate, 3.5 g ofpolyoxyethylene nonyl phenyl ether, 10 g of dipropylene glycolmonomethyl ether and 114 g of ion-exchanged water were charged andpre-emulsified by using a high pressure homogenizer. This emulsion wastransferred to a flask equipped with a stirrer, a thermometer and areflux condenser, nitrogen purge was conducted sufficiently at 60° C.,and then 0.3 g of ammonium persulfate was added to initiate thepolymerization. At 10 hours after the initiation of polymerization, itwas confirmed that 99% of U1 had reacted by gas chromatography and anemulsion having the solid content of 30% was obtained.

PREPARATIVE EXAMPLE 5

35 g of the monomer b (fluorine-containing acrylate) shown in Table 3,10 g of U2 (a urethane bond-containing monomer) synthesized inPreparative Example 2, 5 g of isoprene, 1 g of lauryl mercaptan, 1. 5 gof sodium α-olefin sulfonate, 3.5 g of polyoxyethylene nonyl phenylether, 10 g of dipropylene glycol monomethyl ether and 114 g ofion-exchanged water were charged and pre-emulsified by using a highpressure homogenizer. This emulsion was transferred to a flask equippedwith a stirrer, a thermometer and a reflux condenser, nitrogen purge wasconducted sufficiently at 60° C., and then 0.3 g of ammonium persulfatewas added to initiate the polymerization. At 10 hours after theinitiation of polymerization, it was confirmed that 99% of the monomer bhad reacted by gas chromatography and an emulsion having the solidcontent of 30% was obtained.

PREPARATIVE EXAMPLE 6

Emulsion polymerization was carried out in the same manner as inPreparative Example 5 using the monomer U3 (a urethane bond-containingmonomer) instead of the monomer U2 to give an emulsion having the solidcontent of 30%.

COMPARATIVE PREPARATIVE EXAMPLE 1

35 g of the monomer b (fluorine-containing acrylate) shown in Table 3,15 g of stearyl acrylate, 1 g of lauryl mereaptan, 1.5 g of sodiumα-olefin sulfonate, 3.5 g of polyoxyethylene nonyl phenyl ether, 10 g ofdipropylene glycol monomethyl ether and 114 g of ion-exchanged waterwere charged and pre-emulsified by using a high pressure homogenizer.This emulsion was transferred to a flask equipped with a stirrer, athermometer and a reflux condenser, nitrogen purge was conductedsufficiently at 60° C., and then 0.3 g of ammonium persulfate was addedto initiate the polymerization. At 10 hours after the initiation ofpolymerization, it was confirmed that 99% of the monomer b had reactedby gas chromatography and an emulsion having the solid content of 30%was obtained.

The water and oil repellent compositions obtained in PreparativeExamples 4 to 6 are shown in Table 4.

TABLE 4 Weight ratio of Weight ratio based Preparative A B C D copolymeron polymer Example No. Repeating unit (I) Repeating unit (II) Repeatingunit (III) Film forming auxiliary (B) A/B/C (A + B + C/D) 4 U1 aIsoprene Dipropylene glycol monomethyl 70/20/10 100/20 5 b U2 ether 6 bU3 Comparative b Stearyl acrylate None 70/30/0  100/20 PreparativeExample 1

EXAMPLE 1

Each of the water and oil repellents obtained in Preparative Examples 4to 6 were diluted with water so as to have solid content of 3% and thisliquid was uniformly sprayed on a white cotton broad cloth, a whitepolyester/cotton-blended broad cloth, a white polyester tropical cloth,a white nylon taffeta cloth so as to be 100 g/m². Spray was carried outusing a hand spray. Then, these cloths were dried at room temperaturefor 24 hours. The water and oil repellency test was carried out forthese treated cloths.

The test results are shown in Table 5.

TABLE 5 Water repellency Oil repellency White White White WhitePreparative White cotton polyester/cotton polyester White nylon Whitecotton polyester/cotton polyester White nylon Example No. broad clothbroad cloth tropical cloth taffeta cloth broad cloth broad clothtropical cloth taffeta cloth 4 70+ 80− 80− 70+ 4 4 4 4 5 80− 80  80+ 80−4 4 4 4 6 80− 80+ 80+ 80− 4 4 4 4 Comparative 0 0 0 0 1 1 1 1Preparative Example 1

The preparation of the monomer (I) or (II) having a urethane bond isshown in Preparative Examples 7 to 10.

PREPARATIVE EXAMPLE 7 (PREPARATION OF THE PRODUCT X1)

In a flask equipped with a stirrer, a thermometer, a reflux condenserand a dropping funnel, 200 g of 2,4-tolylene diisocyanate was dissolvedin 441 g of di-n-butyl adipate (DBA) and heated to 40° C. with stirring.When the temperature of the mixture reached 40° C., three drops ofdibutyltin laurate was added and, at the same time, dropwise addition of533 g of perfluoroalkylethyl alcohol (a perfluoroalkyl group isCF₃(CF₂)_(n) (the average of n is 7)) was started and it was gentlyadded dropwise over two hours. After the completion of the dropwiseaddition, 149 g of 2-hydroxyethyl methacrylate was gently added dropwiseover two hours. After the completion of the dropwise addition, thestirring was continued for additional two hours with maintaining at 40°C. to give 1,323 g of pale yellow and transparent viscous liquid.Complete disappearance of a —NCO group was confirmed by IR anddisappearance of a —OH group, formation of a urethane bond and presenceof a double bond were confirmed by ¹H-NMR and ¹³C-NMR. This product wasnamed as X1.

The chemical formula of the product X1 was considered as follows:

wherein Rf is a perfluoroalkyl group.

PREPARATIVE EXAMPLE 8 (PREPARATION OF THE PRODUCT X2) PREPARATIVEEXAMPLE 8 (PREPARATION OF THE PRODUCT X2)

In a flask equipped with a stirrer, a thermometer, a reflux condenserand a dropping funnel, 200 g of 2,4-tolylene diisocyanate was dissolvedin 260 g of di-n-butyl adipate (DBA) and heated to 40° C. with stirring.When the temperature of the mixture reached to 40° C., three drops ofdibutyltin laurate was added and, at the same time, dropwise addition of170 g of dipropylene glycol m6nomethyl ether was started and it wasgently added dropwise over two hours. After the completion of thedropwise addition, 149 g of 2-hydroxyethyl methacrylate was gentlydropped over two hours. After the completion of the dropwise addition,the stirring was continued for additional two hours with maintaining at40° C. to give 779 g of pale yellow and transparent viscous liquid.Complete disappearance of a —NCO group was confirmed by IR anddisappearance of a —OH group, formation of a urethane bond and presenceof a double bond were confirmed by ¹H-NMR and ¹³C-NMR. This product wasnamed as X2.

The chemical formula of the product X2 was considered as the follows:

wherein n is 2.

PREPARATIVE EXAMPLE 9 (PREPARATION OF THE PRODUCT X3)

In a flask equipped with a stirrer, a thermometer, a reflux condenserand a dropping funnel, 200 g of 2,4-tolylene diisocyanate was dissolvedin 217 g of di-n-butyl adipate (DBA) and heated to 40° C. with stirring.When the temperature of the mixture reached to 40° C., three drops ofdibutyltin laurate was added and, at the same time, dropwise addition of85 g of 2-butanol was started and it was gently added dropwise over twohours. After the completion of the dropwise addition, 149 g of2-hydroxyethyl methacrylate was gently dropped over two hours. After thecompletion of the dropwise addition, the stirring was continued foradditional two hours with maintaining at 40° C. to give 651 g of paleyellow and transparent viscous liquid. Complete disappearance of a —NCOgroup was confirmed by IR and disappearance of a —OH group, formation ofa urethane bond and presence of a double bond were confirmed by ¹H-NMRand ¹³C-NMR. This product was named as X3.

The chemical formula of the product X3 was considered as follows:

PREPARATIVE EXAMPLE 10 (PREPARATION OF THE PRODUCT X4)

In a flask equipped with a stirrer, a thermometer, a reflux condenserand a dropping funnel, 200 g of 2,4-tolylene diisocyanate was dissolvedin 250 g of di-n-butyl adipate (DBA) and heated to 40° C. with stirring.When the temperature of the mixture reached to 40° C., three drops ofdibutyltin laurate was added and, at the same time, dropwise addition of150 g of 2-ethyl hexyl alcohol was started and it was gently addeddropwise over two hours. After the completion of the dropwise addition,149 g of 2-hydroxyethyl methacrylate was gently dropped over two hours.After the completion of the dropwise addition, the stirring wascontinued for additional two hours with maintaining at 40° C. to give749 g of pale yellow and transparent viscous liquid. Completedisappearance of a —NCO group was confirmed by IR and disappearance of a—OH group, formation of a urethane bond and presence of a double bondwere confirmed by ¹H-N and ¹³C-NMR. This product was named as X4.

The chemical formula of the product X4 was considered as follows:

The preparation of the water and oil repellent containing the copolymer(A) and the film-forming auxiliary (B) is shown in Preparative Examples11 to 17. In Preparative Examples 11 to 17, in particular the monomersshown in Tables 6 and 7 were used.

TABLE 6 Preparative Preparative Preparative Preparative PreparativeExample 11 Example 12 Example 13 Example 14 Example 15 Copolymer (A)Monomer (I) XI (Preparative Example 7) 71% — — 54% — Monomer b (Table 3)— 55% 54% — 54% Monomer (II) X2 (Preparative Example 8) — — — — — X3(Preparative Example 9) — — — — — X4 (Preparative Example 10) — 45% — —— Monomer a (Table 3) — — — — 23% Monomer (III) Lauryl methacrylate 25%— 46% 46% 23% Monomer (IV) Glucosyl ethyl methacrylate  1% — — — —Monomer (V) 3-Chloro-2-hydroxypropyl methacrylate  3% — — — — Stearylacrylate — — — — — Film-forming Di-n-butyl adipate 36% to (A) 23% to (A)23% to (A) 27% to (A) — auxiliary (B) Butyl carbitol acetate 41% to (A)— — — — Dipropylene glycol monomethyl ether 41% to (A) — — — —

TABLE 7 Comparative Preparative Preparative Preparative PreparativeExample 16 Example 17 Example 18 Example 2 Copolymer (A) Monomer (I) X1(Preparative Example 7) — — — — Monomer b (Table 3) 59% 59% 59% 67%Monomer (II) X2 (Preparative Example 8) 22% — — — X3 (PreparativeExample 9) — 22% — — X4 (Preparative Example 10) — — 22% — Monomer (III)Lauryl methacrylate 15% 15% 15% — Monomer (IV) Glucosyl ethylmethacrylate  1%  1%  1% — Monomer (V) 3-Chloro-2-hydroxypropylmethacrylate  3%  3%  3% — Stearyl acrylate — — — 33% Film-formingauxiliary (B) Di-n-butyl adipate 11% to (A) 11% to (A) 11% to (A) —Butyl carbitol acetate 33% to (A) 33% to (A) 33% to (A) — Dipropyleneglycol monomethyl ether 33% to (A) 33% to (A) 33% to (A) —

PREPARATIVE EXAMPLE 11

27.3 g of X1 (a fluorine-containing monomer, 66.7% di-n-butyl adipatesolution) synthesized in Preparative Example 7, 6.5 g of laurylmethacrylate, 0.8 g of 3-chloro-2-hydroxypropyl methacrylate, 0.3 g ofglucosyl ethyl methacrylate (50% aqueous solution), 1.3 g of laurylmercaptan, 0.4 g of di hardened beef tallow alkyl dimethyl ammoniumchloride (active ingredient of 75%), 5 g of ethanol, 200 g ofion-exchanged water; and 0.1 g of di-n-butyl adipate, 10.6 g of butylcarbitol acetate and 10.4 g of dipropylene glycol monomethyl ether as afilm-forming auxiliary were charged and pre-emulsified by using a highpressure homogenizer. This emulsion was transferred to a flask equippedwith a stirrer, a thermometer and a reflux condenser, nitrogen purge wasconducted sufficiently at 60° C., and then 0.1 g of2,2′-azobis(2-amidinopropane)dihydrochloride was added to initiate thepolymerization. At 5 hours after the initiation of polymerization, itwas confirmed that 99% of X1 had reacted by gas chromatography and anemulsion having the solid content of 10% was obtained.

PREPARATIVE EXAMPLE 12

25.5 g of the monomer b (a fluorine-containing monomer) shown in Table3, 31.5 g of X4 (a urethane bond-containing monomer, 66.7% di-n-butyladipate solution) synthesized in Preparative Example 10, 2.5 g of laurylmercaptan, 0.4 g of stearyl trimethyl ammonium chloride (activeingredient of 30%), 0.6 g of polyoxyethylene octyl phenyl ether, 0.4 gof polyoxyethylene sorbitan monolaurate, 100 g of ion-exchanged waterand 0.4 g of di-n-butyl adipate as a film-forming auxiliary were chargedand pre-emulsified by using a high pressure homogenizer. This emulsionwas transferred to a flask equipped with a stirrer, a thermometer and areflux condenser, nitrogen purge was conducted sufficiently at 60° C.,and then 0.3 g of 2,2′-azobis(2-amidinopropane)dihydrochloride was addedto initiate the polymerization. At 5 hours after the initiation ofpolymerization, it was confirmed that 99% of the monomer b had reactedby gas chromatography and an emulsion having the solid content of 30%was obtained.

PREPARATIVE EXAMPLE 13

25.5 g of the monomer b (a fluorine-containing monomer) shown in Table3, 21.9 g of lauryl methacrylate, 2.5 g of lauryl mercaptan, 0.4 g ofstearyl trimethyl ammonium chloride (active ingredient of 30%), 0.6 g ofpolyoxyethylene octyl phenyl ether, 0.4 g of polyoxyethylene sorbitanmonolaurate, 100 g of ion-exchanged water and 10.9 g of di-n-butyladipate as a film-forming auxiliary were charged and pre-emulsified byusing a high pressure homogenizer. This emulsion was transferred to aflask equipped with a stirrer, a thermometer and a reflux condenser,nitrogen purge was conducted sufficiently at 60° C., and then 0.3 g of2,2′-azobis(2-amidinopropane)-dihydrochloride was added to initiate thepolymerization. At 5 hours after the initiation of polymerization, itwas confirmed that 99% of the monomer b had reacted by gaschromatography and an emulsion having the solid content of 30% wasobtained.

PREPARATIVE EXAMPLE 14

38.2 g of X1 (a fluorine-containing monomer, 66.7% di-n-butyl adipatesolution) synthesized in Preparative Example 7, 21.9 g of laurylmethacrylate, 2.5 g of lauryl mercaptan, 0.4 g of stearyl trimethylammonium chloride (active ingredient of 30%), 0.6 g of polyoxyethyleneoctyl phenyl ether, 0.4 g of polyoxyethylene sorbitan monolaurate, 100 gof ion-exchanged water and 0.1 g of di-n-butyl adipate as a film-formingauxiliary were charged and pre-emulsified by using a high pressurehomogenizer. This emulsion was transferred to a flask equipped with astirrer, a thermometer and a reflux condenser, nitrogen purge wasconducted sufficiently at 60° C., and then 0.3 g of2,2′-azobis(2-amidinopropane)dihydrochloride was added to initiate thepolymerization. At 5 hours after the initiation of polymerization, itwas confirmed that the monomer b of 99% had reacted by gaschromatography and an emulsion having the solid content of 30% wasobtained.

PREPARATIVE EXAMPLE 15

25.5 g of the monomer b (a fluorine-containing monomer) shown in Table3, 11.0 g of the monomer a (a urethane bond-containing monomer) shown inTable 3, 11.0 g of lauryl methacrylate, 2.5 g of lauryl mercaptan, 0.4 gof stearyl trimethyl ammonium chloride (active ingredient of 30%), 0.6 gof polyoxyethylene octyl phenyl ether, 0.4 g of polyoxyethylene sorbitanmonolaurate and 110.9 g of ion-exchanged water were charged andpre-emulsified by using a high pressure homogenizer. This emulsion wastransferred to a flask equipped with a stirrer, a thermometer and areflux condenser, nitrogen purge was conducted sufficiently at 60° C.,and then 0.3 g of 2,2′-azobis(2-amidinopropane)dihydrochloride was addedto initiate the polymerization. At 5 hours after the initiation ofpolymerization, it was confirmed that 99% of the monomer b had reactedby gas chromatography and an emulsion having the solid content of 30%was obtained.

PREPARATIVE EXAMPLE 16

152 g of the monomer b (a fluorine-containing monomer) shown in Table 3and 85 g of X2 (a urethane bond-containing monomer, 66.7% di-n-butyladipate solution) synthesized in Preparative Example 8, 40 g of laurylmethacrylate, 7.5 g of 3-chloro-2-hydroxypropyl methacrylate, 5 g ofglucosyl ethyl methacrylate (50% aqueous solution), 12.5 g of laurylmercaptan, 3.5 g of di hardened beef tallow alkyl dimethyl ammoniumchloride (active ingredient of 75%), 1,250 g of ion-exchanged water; and1 g of di-n-butyl adipate, 86 g of butyl carbitol acetate and 84.5 g ofdipropylene glycol monomethyl ether as a film-forming auxiliary werecharged and pre-emulsified by using a high pressure homogenizer. Thisemulsion was transferred to a flask equipped with a stirrer, athermometer and a reflux condenser, nitrogen purge was conductedsufficiently at 60° C., and then 0.5 g of2,2′-azobis(2-amidinopropane)dihydrochloride was added to initiate thepolymerization. At 5 hours after the initiation of polymerization, itwas confirmed that 99% of the monomer b had reacted by gaschromatography and an emulsion having the solid content of 15% wasobtained.

PREPARATIVE EXAMPLE 17

Emulsion polymerization was carried out in the same manner as inPreparative Example 16 using X3 (a urethane bond containing monomer,66.7% di-n-butyl adipate solution) synthesized in Preparative Example 9instead of X2 (a urethane bond-containing monomer, 66.7% di-n-butyladipate solution) synthesized in Preparative Example 8 to give anemulsion having the solid content of 15%.

PREPARATIVE EXAMPLE 18

Emulsion polymerization was carried out in the same manner as inPreparative Example 16 using X4 (a urethane bond-containing monomer,66.7% di-n-butyl adipate solution) synthesized in Preparative Example 10instead of X2 (a urethane bond-containing monomer, 66.7% di-butyladipate solution) synthesized in Preparative Example 8 to give anemulsion having the solid content of 15%.

COMPARATIVE PREPARATIVE EXAMPLE 2

30 g of the monomer b (a fluorine-containing monomer) shown in Table 3,15 g of stearyl acrylate, 1 g of lauryl mercaptan, 1.5 g of di hardenedbeef tallow alkyl dimethyl ammonium chloride and 114 g of ion-exchangedwater were charged and pre-emulsified by using a high pressurehomogenizer. This emulsion was transferred to a flask equipped with astirrer, a thermometer and a reflux condenser, nitrogen purge wasconducted sufficiently at 60° C., and then 0.3 g of2,2′-azobis(2-amidinopropane)-dihydrochloride was added to initiate thepolymerization. At 5 hours after the initiation of polymerization, itwas confirmed that 99% of the monomer b had reacted by gaschromatography and an emulsion having the solid content of 30% wasobtained.

For the compositions (the water and oil repellents) obtained inPreparative examples 11 to 17 and Comparative Preparative Example 2, thefollowing evaluation was carried out.

EXAMPLE 2

Each of the water and oil repellents obtained in Preparative Examples 11to 17 and Comparative Preparative Example 2 was diluted withion-exchanged water so as to have a solid content of 4% and this liquidwas uniformly sprayed on a white cotton broad cloth, a whitepolyester/cotton-blended broad cloth, a white polyester tropical clothand a white nylon taffeta cloth so as to be 100 g/m². Spray was carriedout using a hand spray (a trigger type container). Then, these clothswere dried at room temperature for 24 hours. The water and oilrepellency test were carried out for these treated cloths. The testresults are shown in Tables 8 and 9.

EXAMPLE 3

Each of the water and oil repellents obtained in Preparative Examples 11to 17 and Comparative Preparative Example 2 was diluted withion-exchanged water so as to have solid content of 4% and this liquidwas charged in an aerosol can. CO₂ as a propellant was further chargedthereto and the container was sealed. The weight ratio of the water andoil repellent to the propellant was 50/50. The aerosol was uniformlysprayed on a white cotton broad cloth, a white polyester/cotton-blendedbroad cloth, a white polyester tropical cloth and a white nylon taffetacloth so as to be 100 g/m², and then these cloths were dried at roomtemperature for 24 hours. The water and oil repellency test was carriedout for these treated cloths. The test results are shown in Tables 8 and9.

EXAMPLE 4

Each of the water and oil repellents obtained in Preparative Examples 11to 17 and Comparative Preparative Example 2 was diluted withion-exchanged water so as to have solid content of 4% and then 1% ofalkyl trimethyl ammonium chloride was added per 100% of the emulsionobtained. This liquid was charged in a container equipped with a nozzlehaving a pore at its ejection port and the treatment agent in the formof foam was propelled from the container. Then, the treatment agent inthe form of foam was placed on a white cotton broad cloth, a whitepolyester/cotton-blended broad cloth, a white polyester tropical clothand a white nylon taffeta cloth, uniformly applied with a sponge so asto be 100 g/m², and then these cloths were dried at room temperature for24 hours. The water and oil repellency test were carried out for thesetreated cloths.

The test results are shown in Tables 8 and 9.

TABLE 8 Preparative Preparative Preparative Preparative PreparativeExample 11 Example 12 Example 13 Example 14 Example 15 Example 2 Waterrepellency White cotton broad cloth 70  80  70+ 70− 70− Whitepolyester/cotton (=65/35) broad cloth 70+ 80  70+ 70  50+ Whitepolyester tropical cloth 80− 80+ 80  80− 50+ White nylon taffeta cloth70+ 80  70+ 70+ 0 Oil repellency White cotton broad cloth 4 4 4 4 3White polyester/cotton (=65/35) broad cloth 4 4 4 4 2 White polyestertropical cloth 4 5 4 4 2 White nylon taffeta cloth 4 6 4 4 1 Example 3Water repellency White cotton broad cloth 70  80  70+ 70  70  Whitepolyester/cotton (=65/35) broad cloth 70+ 80  70+ 70  50+ Whitepolyester tropical cloth 80  80+ 80  80  50+ White nylon taffeta cloth70+ 80  70+ 70+ 0 Oil repellency White cotton broad cloth 4 4 4 4 3White polyester/cotton (=65/35) broad cloth 4 4 4 4 2 White polyestertropical cloth 4 5 4 4 2 White nylon taffeta cloth 4 6 4 4 1 Example 4Water repellency White cotton broad cloth 70− 70+ 70− 70− 50  Whitepolyester/cotton (=65/35) broad cloth 70− 70+ 70− 70− 50  Whitepolyester tropical cloth 70  80+ 70+ 70  0 White nylon taffeta cloth 70−70+ 70  70  0 Oil repellency White cotton broad cloth 4 4 4 4 2 Whitepolyester/cotton (=65/35) broad cloth 4 4 4 4 1 White polyester tropicalcloth 4 5 4 4 1 White nylon taffeta cloth 4 5 4 4 1

TABLE 9 Preparative Preparative Preparative Comparative PreparativeExample 16 Example 17 Example 18 Example 2 Example 2 Water repellencyWhite cotton broad cloth 80+ 90  90  0 White polyester/cotton (=65/35)broad cloth 80+ 90  90  0 White polyester tropical cloth 90− 90  90  0White nylon taffeta cloth 90− 90  90  0 Oil repellency White cottonbroad cloth 5 5 5 1 White polyester/cotton (=65/35) broad cloth 5 5 5 1White polyester tropical cloth 5 6 6 1 White nylon taffeta cloth 5 6 5 1Example 3 Water repellency White cotton broad cloth 80+ 80+ 80+ 0 Whitepolyester/cotton (=65/35) broad cloth 80+ 90  90  0 White polyestertropical cloth 90− 90  90  0 White nylon taffeta cloth 90− 90  90  0 Oilrepellency White cotton broad cloth 5 5 5 1 White polyester/cotton(=65/35) broad cloth 5 5 5 1 White polyester tropical cloth 5 6 6 1White nylon taffeta cloth 5 6 5 1 Example 4 Water repellency Whitecotton broad cloth 80  80+ 80+ 0 White polyester/cotton (=65/35) broadcloth 80  80+ 80+ 0 White polyester tropical cloth 80+ 80+ 80+ 0 Whitenylon taffeta cloth 80+ 80+ 80+ 0 Oil repellency White cotton broadcloth 4 5 5 0 White polyester/cotton (=65/35) broad cloth 4 5 5 0 Whitepolyester tropical cloth 5 5 5 0 White nylon taffeta cloth 5 5 5 0

EFFECTS OF THE INVENTION

The composition of the present invention is superior in processabilityat low temperature and a property of forming a smooth film.

What is claimed is:
 1. A composition comprising (A) a copolymer which comprises (I) repeating units which are derived from a monomer having a fluoroalkyl group, a carbon-carbon double bond, and optionally a urethane or urea bond, (II) repeating units which are derived from a monomer having a urethane or urea bond and one carbon-carbon double bond, but no fluorine atom, (III) repeating units which are derived from a monomer having a carbon-carbon double bond, the homopolymer of said monomer having a glass transition temperature (Tg) of 50° C. or less, (IV) repeating units which are derived from a monomer having a hydrophilic group and a carbon-carbon double bond, and (V) repeating units which are derived from a monomer having a chlorine atom and a carbon-carbon double bond and (B) a film-forming auxiliary consisting of an organic solvent, which dissolves or swells the copolymer, wherein said film-forming auxiliary (B) has a solubility parameter (sp) at 25° C. in the range between 8 and 11, said film-forming auxiliary (B) is at least one solvent selected from the group consisting of alcohols, glycol ethers, linear or cyclic silicones, esters, diesters, ketones and ethers, and the composition is in the form of an aqueous dispersion of the copolymer dispersed in a medium comprising water in the presence of a nonionic, cationic or anionic emulsifier.
 2. A composition according to claim 1, wherein a monomer having no urethane bond, which constitutes said repeating units (I), is a compound of the formula: Rf—R¹—OCO—C (R²)═CH₂ wherein Rf is a linear or branched fluoroalkyl group having 3 to 20 carbon atoms; R¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, a group of the formula: —SO₂N(R³)R⁴— or a group of the formula: —CH₂CH(OR⁵)CH₂— in which R³ is an alkyl group having 1 to 10 carbon atoms, R⁴ is a linear or branched alkylene group having 1 to 10 carbon atoms, and R⁵ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms; and R is a hydrogen atom or a methyl group.
 3. A composition according to claim 1, wherein a monomer having a urethane or urea bond and a fluoroalkyl group, which constitutes said repeating units (I), is a monomer obtained by reacting (I-a) a compound having at least two isocyanate groups, (I-b) a compound having one carbon-carbon double bond and at least one hydroxyl or amino group, and (I-c) a compound having a fluoroalkyl group and one hydroxyl or amino group.
 4. A composition according to claim 1, wherein a monomer which constitutes said repeating units (II) is a monomer obtained by reacting (II-a) a compound having at least two isocyanate groups, and (II-b) a compound having one carbon-carbon double bond and at least one hydroxyl or amino group with (II-c-1) a compound having at least one hydroxyl or amino group, and a polyoxyalkylene chain or a polysiloxane chain, or (II-c-2) a compound having at least one hydroxyl or amino group.
 5. A composition according to claim 1, wherein said repeating units (III) are derived from a monomer having conjugated double bonds or one or two carbon-carbon double bonds, and the homopolymer of which has a glass transition temperature (Tg) of 50° C. or less.
 6. A composition according to claim 1, wherein said repeating units (III) are derived from a monomer, the homopolymer of which has a glass transition temperature (Tg) of 30° C. or less.
 7. A composition according to claim 1, wherein said repeating units (III) are derived from a monomer, the homopolymer of which has a glass transition temperature (Tg) of 0° C. or less.
 8. A composition according to claim 1, wherein said film-forming auxiliary is at least one solvent selected from the group consisting of glycol ethers, esters and diesters.
 9. A composition according to claim 1, which is in the form of an aqueous dispersion of the copolymer dispersed in a medium comprising water in the presence of a cationic emulsifier.
 10. A water and oil repellent comprising a composition as claimed in claim
 1. 11. A method for imparting water and oil repellency to a substrate comprising applying a water and oil repellent as claimed in claim 10 the substrate by spraying, coating or dipping.
 12. A water and oil repellent which is in the form of an emulsion comprising a composition as claimed in claim
 1. 13. A water and oil repellent product comprising a water and oil repellent as claimed in claim 12 and an application apparatus.
 14. A water and oil repellent product comprising a water and oil repellent as claimed in claim 12 which is charged in a container equipped with a mechanism for spraying a liquid outside of said container.
 15. A water and oil repellent product comprising a water and oil repellent as claimed in claim 12 which is charged in a container equipped with a mechanism for propelling a liquid outside of said container using a pressure.
 16. A water and oil repellent in the form of foam or mousse comprising a composition as claimed in claim
 1. 17. A water and oil repellent product comprising a water and oil repellent as claimed in claim 16 which is charged in a container equipped with a mechanism for foaming and propelling a liquid outside of said container.
 18. A method for imparting water and oil repellency to a substrate comprising applying on said substrate the water and oil repellent of claim 12 by spraying, coating or dipping.
 19. A method for imparting water and oil repellency to a substrate according to claim 18 which further comprises dehydrating said substrate after applying the water and oil repellent.
 20. A water and oil repellent in the form of an aerosol comprising a composition as claimed in claim
 1. 21. A water and oil repellent product comprising water and oil repellent as claimed in claim
 20. 22. A water and oil repellent product comprising a water and oil repellent as claimed in claim 20 which is charged in a container equipped with a mechanism for spraying a liquid outside of said container.
 23. A water and oil repellent in the state of a solid comprising a composition as claimed in claim
 1. 24. A water and oil repellent product comprising a water and oil repellent as claimed in claim
 23. 25. A water and oil repellent in the form of a paste comprising a composition as claimed in claim
 1. 26. A water and oil repellent product comprising a water and oil repellent as claimed in claim
 1. 27. A composition comprising (A) a copolymer, which comprises (I) repeating units which are derived from a monomer having a fluoroalkyl group, a carbon-carbon double bond, and optionally a urethane or urea bond, (II) repeating units which are derived from a monomer having a urethane or urea bond and one carbon-carbon double bond, but no fluorine atom, (III) repeating units which are derived from a monomer having a carbon-carbon double bond, the homopolymer of said monomer having a glass transition temperature (Tg) of 50° C. or less, (IV) optional repeating units which are derived from a monomer having a carbon-carbon double bond and a hydrophilic group selected from a carboxyl group, a phosphate group and a sulfate group, or a monomer selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, hydroxypropyl methacrylate trimethylammonium chloride, glucosylethyl methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate and neopentyl glycol hydroxypivalate diacrylate, and (V) optional repeating units which are derived from a monomer having a chlorine atom and a carbon-carbon double bond and (B) a film-forming auxiliary consisting of an organic solvent which dissolves or swells the copolymer, wherein at least one of the repeating units (IV) and the repeating units (V) is essential, said film-forming auxiliary (B) has a solubility parameter (sp) at 25° C. in the range between 8 and 11, said film-forming auxiliary (B) is at least one solvent selected from the group consisting of alcohols, glycol ethers, linear or cyclic silicones, esters, diesters, ketones and ethers, and the composition is in the form of an aqueous dispersion of the copolymer dispersed in a medium comprising water in the presence of a nonionic, cationic or anionic emulsifier.
 28. A composition comprising (A) a copolymer which comprises (I) repeating units which are derived from a monomer having a fluoroalkyl group, a carbon-carbon double bond, and optionally a urethane or urea bond, (II) repeating units which are derived from a monomer having a urethane or urea bond and one carbon-carbon double bond, but no fluorine atom, (III) repeating units which are derived from a monomer having a carbon-carbon double bond, the homopolymer of said monomer having a glass transition temperature (Tg) of 50° C. or less, (IV) optional repeating units which are derived from a monomer having a hydrophilic group and a carbon-carbon double bond, and (V) optional repeating units which are derived from a monomer having a chlorine atom and a carbon-carbon double bond and (B) a film-forming auxiliary consisting of an organic solvent which dissolves or swells the copolymer, wherein at least one of the repeating units (IV) and the repeating units (V) is essential, said film-forming auxiliary (B) has a solubility parameter (sp) at 25° C. in the range between 8 and 11, said film-forming auxiliary (B) is at least one solvent selected from the group consisting of glycol ethers and diesters, and the composition is in the form of an aqueous dispersion of the copolymer dispersed in a medium comprising water in the presence of a nonionic, cationic or anionic emulsifier. 